Journal of Chemical Sciences

, Volume 129, Issue 10, pp 1539–1547 | Cite as

Synthesis, characterization, Hirshfeld surface and theoretical properties of \((\hbox {C}_{7}\hbox {H}_{10}\hbox {N})_{4} [\hbox {H}_{2}\hbox {P}_{2}\hbox {Mo}_{5}\hbox {O}_{23}]\cdot \hbox {H}_{2}\hbox {O}\)

  • Ali Harchani
  • Monika Kučeráková
  • Michal Dušek
  • Amor Haddad
Regular Article
  • 118 Downloads

Abstract

The reaction of molybdic acid, phosphoric acid and copper(II) sulfate pentahydrate with m-toluidine in aqueous solution at room temperature furnished a new diphosphopentamolybdate (\(\hbox {C}_{7}\hbox {H}_{10}\hbox {N})_{4}[\hbox {H}_{2}\hbox {P}_{2}\hbox {Mo}_{5}\hbox {O}_{23}]\cdot \hbox {H}_{2}\hbox {O}\) (1). A single-crystal X-ray diffraction study showed that the compound crystallizes in the triclinic crystal system with space group \(P-1\) and unit cell constants, \(a~=~12.833\) (3) Å, \(b~=~13.9855\) (4) Å, \(c=14.9446\) (4) Å, \(\alpha =64.607\) (3)\({^{\circ }}\), \(\beta ~=~70.578\) (2)\({^{\circ }}\), \(\gamma \) = 65.713 (3)\({^{\circ }}\). The sample was also analyzed by energy dispersive spectroscopy (EDS), infrared spectroscopy (IR) and UV-visible spectroscopy. Using the refined atomic structure, Hirshfeld surface analysis and Semi-empirical calculations were performed to study the intermolecular interactions and calculate theoretical properties of 1.

Graphical Abstract

SYNOPSIS The title compound (\(\hbox {C}_{7}\hbox {H}_{10}\hbox {N})_{4}[\hbox {H}_{2}\hbox {P}_{2}\hbox {Mo}_{5}\hbox {O}_{23}]\cdot \hbox {H}_{2}\hbox {O}\) was synthesized and characterized by IR and UV spectroscopy, and its structure was solved by single crystal X-ray diffraction. The presence of the Mo, P, O, C and N atoms was confirmed by EDS analysis. The Hirshfeld surface analysis was performed to elucidate non-bonding interactions and theoretical properties were calculated.

Keywords

Diphosphopentamolybdate synthesis crystal structure physicochemical properties theoretical study 

Notes

Acknowledgements

This work was supported by the Ministry of Higher Education and Scientific Research of Tunisia. The crystallographic part was supported by the project 15-12653S of the Czech Science Foundation using instruments of the ASTRA lab established within the Operation program Prague Competitiveness - Project CZ.2.16/3.1.00/24510.

Supplementary material

12039_2017_1361_MOESM1_ESM.docx (19 kb)
Supplementary material 1 (docx 19 KB)

References

  1. 1.
    Tohomas J, Kannan K R and Ramanan A 2008 Nanostructured phosphomolybdates J. Chem. Sci. 120 529CrossRefGoogle Scholar
  2. 2.
    Arumuganathan T, Siddikha A and Das S K 2017 ‘Ionic crystals’ consisting of trinuclear macrocations and polyoxometalate anions exhibiting single crystal to single crystal transformation: breathing of crystals J. Chem. Sci. 129 1121CrossRefGoogle Scholar
  3. 3.
    Li S, Li Z, Zhang J, Su Z, Qi S, Guo S and Tan X 2017 Polyoxometalate-based 3D porous framework with inorganic molecular nanocage units J. Chem. Sci. 129 573CrossRefGoogle Scholar
  4. 4.
    Hmida F, Ayed M, Ayed B and Haddad A 2015 Two new inorganic-organic hybrid materials based on inorganic cluster, [\(\text{ X }_{2}\text{ Mo }_{18}\text{ O }_{62}]^{6-}\) (X = P, As) J. Chem. Sci. 127 1645CrossRefGoogle Scholar
  5. 5.
    Miras H N, Yan J, Long D L and Cronin L 2012 Engineering polyoxometalates with emergent properties Chem. Soc. Rev. 41 7403CrossRefGoogle Scholar
  6. 6.
    Qu X, Xu L, Yang Y, Li F and Guo W 2011 Hydrothermal synthesis and crystal structure of (\(\text{ H }_{2}\text{ bpp })_{3}[\text{ Mo }_{5}\text{ P }_{2}\text{ O }_{23}]\text{ H }_{2}\text{ O }\): a twofold interpenetrating 3D supramolecular architecture constructed of Standberg-type polyoxometalate Struct. Chem. 22 965CrossRefGoogle Scholar
  7. 7.
    Ganesan S V and Natarajan S 2005 Hydrothermal synthesis and structure of [(\(\text{ C }_{4}\text{ N }_{2}\text{ H }_{12})_{3}][\text{ P }_{2}\text{ Mo }_{5}\text{ O }_{23}]\cdot \text{ H }_{2}\text{ O }\) and [(\(\text{ C }_{3}\text{ N }_{2}\text{ H }_{12})_{3}][\text{ P }_{2}\text{ Mo }_{5}\text{ O }_{23}\)] \(\cdot \text{4H }_{2}\text{ O }\) J. Chem. Sci. 117 219CrossRefGoogle Scholar
  8. 8.
    Liu H, Wang H, Niu D and Lu Z 2007 Microwave-Assisted Synthesis and Crystal Structure of Molybdophosphate Supramolecular Compound with 2-Aminopyridinium Cations Synth. Reac. Inorg. Met. Org. Nano-Met. Chem. 37 103CrossRefGoogle Scholar
  9. 9.
    Asnani M, Kumar D, Duaisamy T and Ramanan A 2012 Crystallization of organically templated phosphomolybdate cluster-based solids from aqueous solution J. Chem. Sci. 124 1275CrossRefGoogle Scholar
  10. 10.
    Palatinus L and Chapuis G 2007 SUPERFLIP - a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions J. Appl. Crystallogr. 40 786CrossRefGoogle Scholar
  11. 11.
    Petricek V, Dusek M and Palatinus L 2014 Crystallographic Computing System JANA2006: General Features Z. Kristallogr. 229 345Google Scholar
  12. 12.
    Brandenburg K and Putz H 2005 DIAMOND Version 3. Crystal Impact GbR, Postfach 1251, D-53002 Bonn, GermanyGoogle Scholar
  13. 13.
    Spartan 14 2014 Wavefunction Inc. Irvine CA 92,612, USAGoogle Scholar
  14. 14.
    Spackman M A and McKinnon J J 2002 Fingerprinting intermolecular interactions in molecular crystals CrystEngComm 4 378CrossRefGoogle Scholar
  15. 15.
    Wolff S K, Grimwood D J, McKinnon J J, Turner M J, Jayatilaka D aand Spackman M A 2012 CRYSTAL-EXPLORER 3.0 University of Western Australia, PerthGoogle Scholar
  16. 16.
    Jayatilaka D, Grimwood D J and Lee A 2005 TONTO A System for Computational Chemistry (Nedlands: The University of Western Australia)Google Scholar
  17. 17.
    Hirshfeld F L 1977 Bonded-atom fragments for describing molecular charge densities Theor. Chim. Acta 44 129CrossRefGoogle Scholar
  18. 18.
    Luo Y H, Mao Q X and Sun B W 2014 Two new complexes with 6-methylnicotinic acid ligand: Synthesis, crystal structure and Hirshfeld surfaces Inorg. Chim. Acta 412 60CrossRefGoogle Scholar
  19. 19.
    Luo Y H, Sun B W 2013 Pharmaceutical co-crystals of pyrazinecarboxamide (PZA) with various carboxylic acids: crystallography, Hirshfeld surfaces, and dissolution study Cryst. Growth Des. 13 2098CrossRefGoogle Scholar
  20. 20.
    Luo Y H, Xu Band Sun B W 2013 Investigation of supramolecular synthons of p-hydroxybenzoic acid (PHBA): Comparison of its hydrate, co-crystal and salt J. Cryst. Growth 374 88CrossRefGoogle Scholar
  21. 21.
    Desiraju G R and Gavezzotti A 1989 Crystal structures of polynuclear aromatic hydrocarbons Classification, rationalization and prediction from molecular structure. Acta Crystallogr. Sec. B: Struct. Sci. 45 473CrossRefGoogle Scholar
  22. 22.
    Prasad A A, Muthu K, Meenatchi V, Rajasekar M, Agilandeshwari R, Meena K, Manonmoni J V and Meenakshisundaram S P 2015 Optical, vibrational, NBO, first-order molecular hyperpolarizability and Hirshfeld surface analysis of a nonlinear optical chalcone Spectrochim. Acta Part A: Mol. Biomol. Spect. 140 311CrossRefGoogle Scholar
  23. 23.
    Ammari Y, Dhahri E, Rzaigui M, Hlil E K and Abid S 2016 Synthesis, structure and physical properties of an hybrid compound based on Strandberg type polyoxoanions and copper cations J. Clust. Sci. 27 1213CrossRefGoogle Scholar
  24. 24.
    He X, Zhang P, Song T Y, Mu Z C, Yu J H, Wang Y and Xu J N 2004 Hydrothermal synthesis and structure of a molybdenum(VI) phosphate cluster and a three dimensional cobalt molybdenum(V) phosphate Polyhedron 23 2153CrossRefGoogle Scholar
  25. 25.
    Wei C X, Chen J X, Huang Y B, Lan T Y, Li Z S, Zhang W J and Zhang Z C 2006 Syntheses, structures and properties of two molybdenum phosphates [(\(\text{ H }_{20}\text{ P }_{8}\text{ Mo }^{V}_{12}\text{ CdO }_{62}\)) (\(\text{ C }_{4}\text{ H }_{14}\text{ N }_{3})_{2}]\text{2C }_{4}\text{ H }_{13}\text{ N }_{3}\text{8H }_{2}\text{ O }\) and [(\(\text{ H }_{2}\text{ P }_{2}\text{ Mo }^{VI}_{5} \text{ O }_{23})\) (\(\text{ C }_{4}\text{ H }_{14}\text{ N }_{3})\) (\(\text{ C }_{4}\text{ H }_{15}\text{ N }_{3})\) (\(\text{ H }_{3}\text{ O })]\text{3H }_{2}\text{ O }\) J. Mol. Struct. 798 117CrossRefGoogle Scholar
  26. 26.
    Ma Y, Lu Y, Wang E, Xu X, Guo Y, Bai X and Xu L 2006 Hydrothermal synthesis and crystal structure of a novel three-dimensional supramolecular network containing cyclic water hexamers: [\(\text{ Co(en) }_{3}]4[\text{ P }_{2}\text{ Mo }_{5}\text{ O }_{23}]_{2}\text{9H }_{2}\text{ O }\) (en = ethylenediamine) J. Mol. Struct. 784 18CrossRefGoogle Scholar
  27. 27.
    Wang Y, Zhang L C, Zhu Z M, Li N, Deng A F and Zheng S Y 2011 Assembly of four copper(II)–2,2’-biimidazole complex-supported Strandberg-type phosphomolybdates Transit. Met. Chem. 36 261CrossRefGoogle Scholar
  28. 28.
    Nagazi I and Haddad A 2012 Synthesis, characterization and crystal structure of a novel Strandberg-type polyoxoselenomolybdate \(\text{ Rb }_{4}[\text{ Se }_{2}\text{ Mo }_{5}\text{ O }_{21}]\text{2H }_{2}\text{ O }\) Mat. Res. Bull. 47 356CrossRefGoogle Scholar
  29. 29.
    Zhao J W, Li Y Y, Wang Y H, Shi D Y, Luo J and Chen L J 2013 A novel 2D phosphomolybdate hybrid [\(\text{ Cu(En)(EnH) }]_{2}[\text{ P }_{2}\text{ Mo }_{5}\text{ O }_{23}]\text{3H }_{2}\text{ O }\) constructed from strandberg-type polyoxometalate units and copper-organic cation bridges Rus. J. Coord. Chem. 39 519CrossRefGoogle Scholar
  30. 30.
    Sharma S, Brahmachari G, Banerjee B, Nurjamal K, Kumar A K, Srivastava A, Misra N, Pandey S K, Rajnikant and Gupta V K 2016 Synthesis, spectroscopic characterization and crystallographic behavior of a biologically relevant novel indole-fused heterocyclic compound — Experimental and theoretical (DFT) studies J. Mol. Struct. 1118 344Google Scholar
  31. 31.
    Soria-Martínez R, Mendoza-Merono R and García-Granda S 2016 Synthesis, crystal structure, spectroscopic characterization and theoretical study of (2E)-N-phenyl-2-(pyridin-3-ylmethylidene)hydrazinecarboxamide J. Mol. Struct. 1105 322CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2017

Authors and Affiliations

  • Ali Harchani
    • 1
  • Monika Kučeráková
    • 2
  • Michal Dušek
    • 2
  • Amor Haddad
    • 1
  1. 1.Laboratoire de Matériaux, Cristallochimie et de ThermodynamiqueAppliquée. Université Tunis El Manar, Faculté de Sciences de Tunis. Université de Monastir, Faculté des Sciences MonastirMonastirTunisia
  2. 2.Institute of Physics ASCRPraha 8Czech Republic

Personalised recommendations